Photoelectrochemical pumping of enzymatic CO2 reduction

Parkinson, B. A.; Weaver, Paul F.

doi:10.1038/309148a0

Cited by 250 publications

(121 citation statements)

References 16 publications

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“…Preliminary attempts to use a ruthenium catalyst to reduce CO 2 to formate electrochemically required similarly high overpotentials and also led to a mixture of products (29). Formate dehydrogenase from Pseudomonas oxalaticus was applied also to the electrochemical reduction of CO 2 (25). However, it was present in solution at high concentration, and electron transfer between the enzyme and the electrode was mediated by millimolar concentrations of methyl viologen (comparable with the concentrations of formate generated), with variable Faradaic efficiency.…”

Section: Discussionmentioning

confidence: 99%

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme

Reda

Plugge

Abram

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

487

420

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Carbon dioxide (CO2) is a kinetically and thermodynamically stable molecule. It is easily formed by the oxidation of organic molecules, during combustion or respiration, but is difficult to reduce. The production of reduced carbon compounds from CO 2 is an attractive proposition, because carbon-neutral energy sources could be used to generate fuel resources and sequester CO 2 from the atmosphere. However, available methods for the electrochemical reduction of CO2 require excessive overpotentials (are energetically wasteful) and produce mixtures of products. Here, we show that a tungsten-containing formate dehydrogenase enzyme (FDH1) adsorbed to an electrode surface catalyzes the efficient electrochemical reduction of CO 2 to formate. Electrocatalysis by FDH1 is thermodynamically reversible-only small overpotentials are required, and the point of zero net catalytic current defines the reduction potential. It occurs under thoroughly mild conditions, and formate is the only product. Both as a homogeneous catalyst and on the electrode, FDH1 catalyzes CO 2 reduction with a rate more than two orders of magnitude faster than that of any known catalyst for the same reaction. Formate oxidation is more than five times faster than CO 2 reduction. Thermodynamically, formate and hydrogen are oxidized at similar potentials, so formate is a viable energy source in its own right as well as an industrially important feedstock and a stable intermediate in the conversion of CO2 to methanol and methane. FDH1 demonstrates the feasibility of interconverting CO2 and formate electrochemically, and it is a template for the development of robust synthetic catalysts suitable for practical applications.electrocatalysis ͉ formate dehydrogenase ͉ formate oxidation ͉ protein film voltammetry ͉ carbon dioxide reduction C arbon dioxide (CO 2 ) is a kinetically and thermodynamically stable molecule that is difficult to chemically activate. As the unreactive product of the combustion of carbon-containing molecules, such as fossil fuels, and biological respiration, it is accumulating in the atmosphere and is a major cause of concern in climate-change scenarios (1, 2). Consequently, catalysts that are able to sequester CO 2 from the atmosphere rapidly and efficiently, to generate reduced carbon compounds for use as fuels or chemical feedstocks, have long been sought after. Organometallic complexes that insert CO 2 into an M-H bond and the use of supercritical CO 2 to facilitate its hydrogenation are two promising approaches to the development of a homogeneous catalytic process (3-5). Extensive efforts to develop electrode materials for the direct, electrochemical reduction of CO 2 have been made also, but so far, they require the application of extreme potentials (are inefficient energetically) or they are nonspecific and produce mixtures of products (4, 6, 7). An efficient and specific method for reducing CO 2 electrochemically has obvious applications in a future energy economy based on the cyclic reduction and oxidation of simple carbon compound...

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Section: Discussionmentioning

confidence: 99%

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme

Reda

Plugge

Abram

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

487

420

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“…30 One of the earliest successful photoelectrochemical systems for the reduction of CO 2 was based on an InP semiconductor/methyl viologen (MV)/formate dehydrogenase (FDH) enzyme system. 31 Light from a tungsten-halogen lamp illuminated InP, reducing MV 2+ to MV + . The MV + served as a mediator, reducing the FDH enzyme, which subsequently reduced dissolved CO 2 to HCOOH with current efficiencies between 89-93% and 21,000 turnovers.…”

Section: Semiconductor Photocatalytic Activation and Fixation Of Comentioning

confidence: 99%

Artificial photosynthesis: semiconductor photocatalytic fixation of CO2 to afford higher organic compounds

2011

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“…Elegant advances in traditional approaches to CO 2 reduction driven by electrical and/or solar inputs using homogeneous (4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16), heterogeneous (17)(18)(19)(20)(21)(22)(23)(24)(25)(26), and biological (7,(27)(28)(29)(30)(31) catalysts point out key challenges in this area, namely (i) the chemoselective conversion of CO 2 to a single product while minimizing the competitive reduction of protons to hydrogen, (ii) long-term stability under environmentally friendly aqueous conditions, and (iii) unassisted light-driven CO 2 reduction that does not require external electrical bias and/or sacrificial chemical quenchers. Indeed, synthetic homogeneous and heterogeneous CO 2 catalysts are often limited by product selectivity and/or aqueous compatibility, whereas enzymes show exquisite specificity but are generally less robust outside of their protective cellular environment.…”

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confidence: 99%

Hybrid bioinorganic approach to solar-to-chemical conversion

Nichols

Gallagher

Liu

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

254

187

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Natural photosynthesis harnesses solar energy to convert CO 2 and water to value-added chemical products for sustaining life. We present a hybrid bioinorganic approach to solar-to-chemical conversion in which sustainable electrical and/or solar input drives production of hydrogen from water splitting using biocompatible inorganic catalysts. The hydrogen is then used by living cells as a source of reducing equivalents for conversion of CO 2 to the value-added chemical product methane. Using platinum or an earth-abundant substitute, α-NiS, as biocompatible hydrogen evolution reaction (HER) electrocatalysts and Methanosarcina barkeri as a biocatalyst for CO 2 fixation, we demonstrate robust and efficient electrochemical CO 2 to CH 4 conversion at up to 86% overall Faradaic efficiency for ≥7 d. Introduction of indium phosphide photocathodes and titanium dioxide photoanodes affords a fully solar-driven system for methane generation from water and CO 2 , establishing that compatible inorganic and biological components can synergistically couple light-harvesting and catalytic functions for solar-to-chemical conversion.artificial photosynthesis | solar fuels | photocatalysis | carbon dioxide fixation | water splitting M ethods for the sustainable conversion of carbon dioxide to value-added chemical products are of technological and societal importance (1-3). Elegant advances in traditional approaches to CO 2 reduction driven by electrical and/or solar inputs using homogeneous (4-16), heterogeneous (17-26), and biological (7, 27-31) catalysts point out key challenges in this area, namely (i) the chemoselective conversion of CO 2 to a single product while minimizing the competitive reduction of protons to hydrogen, (ii) long-term stability under environmentally friendly aqueous conditions, and (iii) unassisted light-driven CO 2 reduction that does not require external electrical bias and/or sacrificial chemical quenchers. Indeed, synthetic homogeneous and heterogeneous CO 2 catalysts are often limited by product selectivity and/or aqueous compatibility, whereas enzymes show exquisite specificity but are generally less robust outside of their protective cellular environment. In addition, the conversion of electrosynthetic systems to photosynthetic ones is nontrivial owing to the complexities of effectively integrating components of light capture with bond-making and bond-breaking chemistry.Inspired by the process of natural photosynthesis in which lightharvesting, charge-transfer, and catalytic functions are integrated to achieve solar-driven CO 2 fixation (32-35), we have initiated a program in solar-to-chemical conversion to harness the strengths inherent to both inorganic materials chemistry and biology (36). As shown in Fig. 1, our strategy to drive synthesis with sustainable electrical and/or solar energy input (37) interfaces a biocompatible photo(electro)chemical hydrogen evolution reaction (HER) catalyst with a microorganism that uses this sustainably generated hydrogen as an electron donor for CO 2 reduction. Impo...

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Photoelectrochemical pumping of enzymatic CO2 reduction

Cited by 250 publications

References 16 publications

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme

Artificial photosynthesis: semiconductor photocatalytic fixation of CO2 to afford higher organic compounds

Hybrid bioinorganic approach to solar-to-chemical conversion

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